Photographic elements comprising merocarbocyanine filter dyes

ABSTRACT

There are disclosed merocarbocyanine filter dyes of the formula   These dyes are characterized by a rapid rate of bleaching in sulfite solutions of the type conventionally used in photographic developing solutions.

United States Patent [191 Sauter Oct. 8, 1974 PHOTOGRAPHIC ELEMENTS COMPRISING MEROCARBOCYANINE FILTER DYES [75] Inventor: Frederick J. Sauter, Rochester,

[73] Assignee: Eastman Kodak Company,

Rochester, NY.

22 Filed: June 26, 1972 21 Appl. No.: 266,028

[52] US. Cl 96/84 R, 117/333, 252/300, 260/240.4

[51] Int. Cl G030 1/84 [58] Field of Search 96/84 R; 117/333; v 252/300 [56] References Cited UNITED STATES PATENTS 1/1950 Brooker et a1. 96/84 R 4/1969 Heseltine 96/84 R 4/1969 Holtzclaw et al. 96/140 8/1972 Jenkins et al. 96/804 R Primary Examiner-Ronald H. Smith Attorney, Agent, or Firm-M. R. Chipolowski [57] ABSTRACT There are disclosed merocarbocyanine filter dyes of the formula bleaching in sulfite solutions of the type conventionally used in photographic developing solutions.

8. Claims, N0 Drawings PHOTOGRAPHIC ELEMENTS COMPRISING MEROCARBOCYANINE FILTER DYES This invention relates to photographic filter dyes having accelerated rates of bleaching. This invention also relates to photographic elements comprising a support having thereon at least one layer containing such filter dyes.

It is known that photographic elements require for many purposes to have light-screening substances incorporated therein. In particular, light-screening substances are often required (a) in overcoatings upon photographic elements to protect the light sensitive emulsion or emulsions from the action of light which it is not desired to record, ([2) in layers arranged between differentially colored sensitized emulsions, e.g., to protect redand green-sensitive emulsions from the action of blue light, and (c) in backings forming the-so-called antihalation layers on either side of a transparent supwherein R, represents a lower alkyl group having 1 to 8 carbon atoms such as methyl, ethyl, propyl, butyl, etc., and including substituted lower alkyl groups such as a carboxyalkyl group (e.g., carboxymethyl, carboxyethyl, carboxypropyl, carboxybutyl, etc.), a alkoxycarbonylalkyl group (e.g., methoxycarbonylmethyl, ethoxycarbonylethyl, propoxycarbonylethyl, propoxycarbonylbutyl, etc.), a sulfoalkyl group (e.g., sulfomethyl, sulfoethyl, sulfopropyl, sulfobutyl, etc.), a hydroxyalkyl group (e.g., hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, etc.), an alkoxyalkyl group (e.g., methoxyethyl, methoxypropyl, ethoxyethyl, ethoxypropyl, etc.), a sulfoalkoxyalkyl group; an aryl group such as phenyl, 4-methylphenyl, 4-chlorophenyl, etc.; or an electron withdrawing group (e.g., a cyanoalkyl group or an acylalkyl group) and G represents a hydrogen atom or an electron withdrawing group such as a sulfamoyl group (e.g., the group R- CONHSO or R NHSO wherein R and R each represents a lower alkyl group or aryl group as previously defined for R at least one of the groups R and G being an electron withdrawing group.

The merocarbocyanine dyes of this invention maybe prepared by heating a mixture of a quaternary ammonium salt having the formula wherein R and G are as previously defined, R represents a 2-anilinovinyl group or a 2-acetanilidovinyl group, and A is an anionic group such as chloride, bromide, iodide, p-toluenesulfonate, thiocyanate, perchlorate, acetate, methylsulfate, ethylsulfate, etc., with 6- methyl-2H-pyran-2,4(3H)-dione. The reaction may be carried out in the presence of an inert solvent such as pyridine, quinoline, isoquinoline, ethanol, n-propanol, n-butanol, etc. and in the presence of a basic condensing agent such as the trialkyl amines (e.g., triethylamine, tri-n-propylamine, tri-n-butylamine, etc.), N- methylpiperidine, N-ethylpiperidine, N.N- dimethylaniline, etc.

The quaternary ammonium salts of Formula ll wherein G is a sulfamoyl group may be prepared by reacting 2-methyl-6-chlorosulfonylbenzoxazole with an appropriate amine to form a -sulfarnoyl derivative, thereafter preparing the quaternary salt and then converting the Z-methyl group to a 2-anilinovinyl group or 2-acetanilidovinyl group by known methods. The following examples illustrate the preparation of some qua ternary ammonium salts of Formula I] wherein G is the electron withdrawing group:

EXAMPLE A A mixture of 2-methylbenzoxazole g.) and chlorosulfonic acid (350 ml.) is heated to a temperature of l45-150C. in an oil bath for l-% hours. The mixture is then cooled and quenched on 2 kg. of crushed ice. The resultant precipitated solid is dissolved in ether, filtered, dried and concentrated to give l2l g. (70 percent yield) of crude 6-chlorosulfonyl-2- methylbenzoxazole having the formula This product (16.2 g.) is added with stirring to a mixture of ml. of diethyl ether and 50 ml. of concentrated aqueous ammonia. The resultant precipitated solid is filtered off and recrystallized from ethanol (250 ml.) to afford 5.9 g. (42 percent yield) of crystalline 2- methyl-6-sulfamoylbenzoxazole having the formula (IV) N H2S O 2 o The product IV has a melting point of 2072l0.5C.

orb-@5103- diethyl ether to the reaction mixture and is obtained in 45 percent yield with a melting point above 250C. it is heated with diphenylformamidine to form 2-(2- anilinovinyl)-3-methyl-6-N-phenylsulfamoylbenzoxazolium p-toluenesulfonate.

EXAMPLE C The procedure of Example B is repeated except that ethylamine is substituted for the aniline to obtain 2- methyl-6-(N-ethylsulfamoyl)benzoxazole, having a melting point of 97-98C., which after heating with methyl-p-toluenesulfonate yields the quaternary salt Vl C2H5NHSO in 33 percent yield having a melting point of 190C. It is heated with diphenylformamidine to form 2-(2- anilinovinyl)-3-methyl-6-N-ethylsulfamoylbenzoxazolium p-toluenesulfonate.

EXAMPLE D v11 7 v moomrsoZ fo al -OH=OHN\ \& CaHa EXAMPLE E 2-( Z-Acetanilidovinyl )-3-( 2-cyanoethyl )benzothiazolium bromide ar ornomcN To a solution of N,N-diphenylformamidine (2.20 g., 1.1 mmoles) in 7 ml. acetic anhydride is added 3-(2- cyanoethyl)-Z-methyl-benzoxazolium bromide (2.45 g., 0.92 mmoles), and the mixture was heated with stirring to 100C. until all the solid material had dissolved. The reaction mixture was cooled, and the product was precipitated by the addition of diethyl ether. After stirring 16 hours under diethyl ether, the solid product was collected by filtration and dried. The yield was 2.0 g.

The merocarbocyanine filter dyes of this invention are more rapidly bleached in buffered alkaline sulfite solutions of the type conventionally used in photographic developing solutions than analogous compounds which do not contain electron withdrawing groups. For example, dyes of Formula I wherein R is a cyanoethyl group or a phenacyl group are more rapidly bleached than are the corresponding N-sulfoalkyl or N-ethyl substituted dyes. The dyes of Formula I wherein R, is a cyanoethyl group are bleached up to 27 times faster than analogous compounds wherein R is a sulfopropyl group.

The merocarbocyanine filter dyes can be incorporated into various layers of the photographic element by methods well known in the art, e.g., by coating on a photographic base a water solution of the dye and a hydrophilic colloid binder. Hydrophilic colloids which can be used as vehicles for the present dyes are those known to be satisfactory vehicles for use in making photographic elements and include emulsions comprising both naturally-occurring substances such as proteins, for example, gelatin, gelatin derivatives, cellulose derivatives, polysaccharides such as dextran, gum arabic and the like; and synthetic polymeric substances such as water soluble polyvinyl compounds like poly(- vinylpyrrolidone), acrylamide polymers and the like. The proportions of dye and colloid binders may be varied over wide ranges and will depend upon the specific requirements of the photographic element being produced. The method used to determine-the optimum composition is well known in the art.

Light sensitive layer or layers and the filter dye layer of the invention can be coated on any suitable support. Typical supports include cellulose nitrate film, cellulose acetate film, poly(vinyl acetal) film, polystyrene film, poly(ethylene terephthalate) film, polycarbonate film and related films or resinous materials, as well as glass, paper, metal and the like. Typically, a flexible support is employed, especially a paper support, which can be partially acetylated or coated with baryta and/or an alpha-olefin polymer, particularly a polymer of an alpha-olefin containing 2 to 10 carbon atoms such as polyethylene, polypropylene, ethylenebutene copolymers and the like.

The photograhic elements utilizing the present merocarbocyanine filter dye layers can have light-sensitive silver halide emulsion layers containing, for example, silver chloride, silver bromide, silver bromoiodide, silver chlorobromide, silver chloroiodide, silver chlorobromoiodide crystals or mixtures thereof. The emulsions can be coarse or fine grain emulsions and can be prepared by a variety of techniques, e.g., single jet emulsions such as those described in Trivelli and Smith The Photographic Journal, Vol. LXXIX, May 1939 (pp. 330-338), double jet emulsions such as Lippmann emulsions, ammoniacal emulsions, thiocyanate or thioether ripened emulsions such as those described in Neitz et al U.S. Pat. No. 2,222,264, issued Nov. 19, 1940; Illingsworth U.S. Pat. No. 3,320,069 issued May 17, 1967 and McBride U.S. Pat. No. 3,271,157 issued Sept. 6, 1966. Conventional silver halide emulsion addendacan be added to such emulsions and include those disclosed in Product Licensing Index, Vol. 92, December 1971, publication 9232, pages 107-l09, particularly paragraphs Ill-VII, XI-XII and XV.

The following examples further illustrate the inventron.

EXAMPLE 1 Cyanoethyl)benzoxazolinylidene ]ethylidene}-6- methyl-2H-pyran-2,4( 3H )-dione 2-(2-Acetanilidovinyl)-3-(2-cyanoethyl)- benzoxazolium bromide (0.40 g., 1.00 m. mole), acetic anhydride (0.5 ml.) and '6methyl-2H-pyran- 2,4(3H)dione (0.14 g., 1.11 m. mole) are stirred in 3 ml. of dimethylformamide. Triethylamine (0.3 ml.) is then added and the reaction is stirred until no further product crystallizes out. The crude dye, 0.25 g., is collected, washed with acetonitrile and recrystalliZed twice from ethanol (400 ml. of ethanol per g. of product) to yield 0.18 g. of dye. The product has a melting point of 253C., a A in methanol of 451 nm. and a bleach rate of 2.7 k Mols see.

o k I -CHCH f CH1 0 0 e011. 0

secf.

EXAMPLE 3 3-[(6-acety1sulfamoyl-3-methyl-2- benzoxazolinylidene)-ethylidene]-6 methyl-2H pyran-2,4(3H)-dione 0 v 0 011.0 ONHSOz OIL-CH l I? 0 Ha 6 EXAMPLE 4 3-[ 6-N-pheny1sulfamoyl-3-methyl-2- benzoxazolinylidene)ethylidenel-ZH-pyran- 6 91299.

aHsNHSOr This product is obtained by the process of Example 1 substituting 2-(2-anilinovinyl)-3-methyl-6-N- phenylsulfamoylbenzoxazolium bromide for the 2 (2- anilinovinyl)-3-(2-cyanoethyl)-benzoxazolium bromide and using ethanol as the reaction solvent instead of dimethylformamide and pyridine as the recrystallization solvent instead of ethanol. The product has a melting point above 260C, a A in a mixture of methanol and pyridine of 457 nm. and a bleach rate of 2.4 k Mol' see. EXAMPLE 5 3-[(6-N-Ethylsulfamoyl-3-methyl-2- benzoxazolinylidene)ethylidenel-6-methyl CgHiNHS O .O CH: O

This product is obtained by the process of Example 1 substituting 2-(2-anilinovinyl)-3-methyl-6-N- ethylsulfamoylbenzoxazolium bromide for the 2-(2- anilinovinyl)-3-(2-cyanoethyl)-benzoxazolium bromideand using a mixture of cresol and ethanol as the recrystallization solvent instead of ethanol. The product has a melting point above 280C, a A in a mixture of cresol and methanol of 455 nm. and a bleach rate of 18.0 k Mols secf.

EXAMPLE 6 The dyes of Examples 1, 3, 4 and 5 dissolved in suitable solvents, are added to separate portions of an aqueous gelatin solution containing saponin as a spreading agent. The dyes of Examples 1, 2, 4 and 5 are dissolved in a mixture of N-methylpyrrolidone and acetone and the dye of Example 3 is dissolved in a mixture of methanol and triethylamine. Each solution is coated at a coverage of about 10 mg. of dye per square foot and about 800 mg. of gelatin per square foot on a cellulose acetate photographic film support and the coatings are dried. The optical densities of the coatings are measured spectrophotometrically, fresh (before soaking in water), after soaking for 5 minutes in water, after soaking for 5 minutes in water and 3 minutes in Kodak D-l9 developer, and after soaking for 5 minutes in water, 3 minutes in Kodak D-19 developer and 5 minutes in Kodak F-5 fixer, and the results are recorded in the Table. The column headed After Inc." records the optical density of untreated coating after incubation at C. for 7 days. The values in the column headed Percent After Inc. are determined by dividing the value for After Inc. by the value for Fresh."

TABLE Optical Density at A After Soaking After Soaking Min. in Water. Dye of A After Soaking 5 Min. in Water and 3 Min. in Developer After After Example (nm) Fresh 5 Min. in Water 3 Min. in Developer and 5 Min. in Fixer c. Inc.

dye decomposed "peak at 350nm As used herein the empirical formulas -C H and -C,,H,, refer to ethyl and phenyl respectively.

The invention has been described in detail with particular reference to preferred embodiments thereof, but, it will be understood that variations and modifications can be effected within the spirit and scope of the invention.

1 claim:

1. A photographic element comprising a support having thereon at least one layer containing a lightsensitive material and at least one layer containing a merocarbocyanine filter dye having the formula wherein R, represents a lower all yl group, an aryl group, a cyanoalkyl group, or an acylalkyl group and G represents a hydrogen or a sulfamoyl group, at least one of the groups R, and G being an electron withdrawing group.

2. A photographic element comprising a support having thereon at least one layer containing a lightsensitive material and at least one layer containing a merocarbocyanine filter dye having the formula O :CHCH I wherein G represents a hydrogen atom and R, is a cyanoalkyl group or an acylalkyl group.

3. A photographic element comprising a support having thereon at least one layer containing a lightsensitive material and at least one layer containing a merocarbocyanine filter dye having the formula wherein R, represents a lower alkyl group or an aryl group and G represents a sulfamoyl group.

4. A photographic element as defined in claim 1 wherein said filter dye is 3-{ [3-( 2- cyanoethyl)benzoxazolinylidene]ethylidene}-6- methyl-2H-pyran-2,4( 3 H )-dione.

5. A photographic element as defined in claim 1 wherein said filter dye is 6-methyl-3-[(3-phenacyl-2- benzoxazolinylidene)-ethylidene]-2H-pyran-2,4(3H)- dione.

6. A photographic element as defined in claim 1 wherein said filter dye is 3-[(6-acetysulfamoyl-3- methyl-2-benzoxazolinylidene)-ethylidene]-6-methyl- 2l-l-pyran-2,4(3H)-dione.

7. A photographic element as defined in claim 1 wherein said filter dye is 3-[(6-N-phenylsulfamoyl-3- methyl-2-benzoxazolinylidene)ethylidene]-2H-pyran- 2,4(3H)-dione.

8. A photographic element as defined in claim 1 wherein said filter dye is 3-[(6-N-ethylsulfamoyl-3- methyl-2-benzoxazolinylidene)ethylidene]-6-methyl- 2H-pyran-2,4(3H)-dione. 

1. A PHOTOGRAPHIC ELEMENT COMPRISING A SUPPORT HAVING THEREON AT LEAST ONE LAYER CONTAINING A LIGHT-SENSITIVE MATERIAL AND AT LEAST ONE LAYER CONTAINING A MEROCARBOCYANINE FILTER DYE HAVING THE FORMULA
 2. A photographic element comprising a support having thereon at least one layer containing a light-sensitive material and at least one layer containing a merocarbocyanine filter dye having the formula
 3. A photographic element comprising a support having thereon at least one layer containing a light-sensitive material and at least one layer containing a merocarbocyanine filter dye having the formula
 4. A photographic element as defined in claim 1 wherein said filter dye is 3-((3-(2-cyanoethyl)benzoxazolinylidene)ethylidene)-6-methyl-2H-pyran-2, 4(3H)-dione.
 5. A photographic element as defined in claim 1 wherein said filter dye is 6-methyl-3-((3-phenacyl-2-benzoxazolinylidene)-ethylidene)-2H-pyran-2,4(3H) -dione.
 6. A photographic element as defined in claim 1 wherein said filter dye is 3-((6-acetysulfamoyl-3-methyl-2-benzoxazolinylidene)-ethylidene)-6-methyl-2H-pyran-2,4(3H)-dione.
 7. A photographic element as defined in claim 1 wherein said filter dye is 3-((6-N-phenylsulfamoyl-3-methyl-2-benzoxazolinylidene)ethylidene)-2H-pyran -2,4(3H)-dione.
 8. A photographic element as defined in claim 1 wherein said filter dye is 3-((6-N-ethylsulfamoyl-3-methyl-2-benzoxazolinylidene)ethylidene)-6-methyl -2H-pyran-2,4(3H)-dione. 